IL25982A - 5-sulphonyl-1,2-dithiol-3-one compounds,their preparation - Google Patents

Description

AGRIPATS.A.

CH 4000 Basel 21 (Schweiz/Switzerland) 2200* Process for the production of new 5-sulphonyl-l ,2-dithio]-3- ones and their use for the combatting of fungi and bacteria The present invention concerns processes for the production of new 5-sulphonyl-l , 2-dithiol-3-ones , fungicidal and bac- 5 tericidal agents which contain these new compounds as active substances, processes for combatting injurious fungi and bacteria (micro-organisms) using the new 1 ,2-dithio-3-ones or agents containing them and also the objects and materials protected from attack by fungi and bacteria by treatment with such compounds.

It is known from the literature that the ring system of 1 , 2-dithiol-3-one may be, extraordinarily easily broken by nucleo- philic reactants, especially in a strong alkaline medium, [F. Bo- berg, Liebigs Ann. Chem. 666, 88 (1963); 679, 118 (1964); Angew.

Chem. 73, 579 (1961); 74, 495 (1962); 76, 575 (1964)]. An ex- 15 change of the chlorine atom in the 5-position in 5-chloro-l , 2-di- thiol-3-ones for other radicals while maintaining the ring system is thus difficult and up to now has only been described for the radicals of certain amines; in this exchange reaction also, generally the greater part of the 5-chloro-l , 2-dithiol-3-one used is decomposed by ring breakage [F. Boberg and A. Marei, Liebigs Ann.

Chem. 666, 88 (1963); F. Boberg, Liebigs Ann. Chem. 681, 169 (1965)].

Surprisingly it has now been found that 5-chloro-l , 2-di- thiol-3-ones react with salts of organic sulphinic acids which are 25 also nucleophilic reactants, without the heterocyclic ring system being broken. The reaction proceeds extraordinarily easily with - 2 - 25982/2 the exchange of the chlorine atom in the 5-position for a sulphonyl radical.

The process according to the invention for the production of new 5-sulphonyl-l , 2-dithiol-3-ones of general formula I wherein fi^ represents halogen, phenyl or lo'or alkyl-a bs it ted phenyl, and Rg represents a straight or branched alkyl radical, optionally mono- or poly-substituted by halogen, hydroxyl, carboxyl, alkoxy-carbonyl, phenyl, alkoxy, acylamino, alkylamlno, dialkylamino, alkylphenyl or halogenphenylj an aromatic radical optionally mono- or poly-substituted by hydroxyl, amino, nitro, cyano, carboxyl, carbamoyl, halogen, alkyl (straight or branched chain) having 1 to 9 carbon atoms, phenyl, phenoxy, alkoxy, alkylthio, alkylamino, dialkylamino or alkanoylamino; or the thienyl radical, is characterised by reacting a l,2-dithiol-3-one of the general has the meaning given in formula I, and X represents a halogen atom, with a sulphinic acid salt of the general formula III ¾ - S02 - Q III wherein R2 has the meaning given in formula I, and the reaction preferably being performed in the presence of a solvent or diluent. As solvents water, organic solvents such as aromatic hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, alcohols, ethers, amides, sulphoxides and also mixtures of water and such solvents can be used. As sulphinic acid salts of the general formula III, in particular the alkali and alkaline earth metal salts, also the ammonium salts of the corresponding sulphinic acids are used for the reaction; however, also other metal salts such as the iron, copper, zinc or aluminium salts can be used.

The new active substances of general formula I can also be produced by oxidising a sulphide of 1 , 2-dithiol-3-one of the general formula IV wherein R-^ und R^ have the meanings given in formula I, into a sulphonyl compound of the general formula I. Hydrogen peroxide, organic per-acids such as peracetic acid, or potassium permanganate, for example, are used as oxidising agents.

Compounds of the general formula IV are obtained in poor yields by reacting in an alkaline medium a 5-halogen-l , 2-dithiol -3-one with a salt of the formula R2SZ wherein R2 has the meaning given above and Z is the equivalent of a metal atom cation.

If is a halogen atom, chlorine is the preferred halogen. A phenyl radical symbolised by R-. can optionally be sub- or an alkyl radical stituted by feai©g.e^ ^-$>a^^-«^ OP-■·<¾*¾·-ar¾»y-l--p-a --e-e-¾l having from 1 to 4 carbon atoms. te&v %-££Qm-l-lj^^£.ax £t£^£dJXii^ By alkyl radicals R2 are meant those having, preferably, 1 to 10 carbon atoms in a straight or branched chain which can carry for example at least one of the following substituents: halogen, hydroxyl , carboxyl , alkoxy-carbonyl, phenyl, alkoxy, acylamino, alkylamino, dialkylamino, alkyl henyl or halogenphenyl .

By optionally substituted aromatic radicals R2 are meant in particular the phenyl radical, a naphthyl radical and also a radical of tetralin. These radicals can be mono- or poly-sub- I ! stituted by the following substituents: hydroxyl, amino, nitro, cyano, carboxyl, carbamoyl, halogen, alkyl (straight or branched chain) having 1 to 9 carbon atoms, phenyl, phenoxy, alkoxy, alkyl thio, alkylamino, dialkylamino or alkanoylamino .

Because of their excellent fungicidal and bactericidal activity, the new 5-sulphonyl-l , 2-dithiol-3-ones of general formula I are suitable for the combatting of phytopathogenic fungi on plants and of fungi and bacteria which injure and' destroy organic materials and useful objects. The new compounds have earth-fungicidal and nematicidal properties so that they can be used for earth desinfection.

The new active substances of general formula I are active against numerous phytopathogenic fungi. They can thus serve for the protection of plants or parts thereof such as blossom, seeds fruit, roots, stems and foliage, from attack by fungi as well as for the combatting of such fungi on these parts of plants. The new compounds act also as systemic fungicides. Because of this property, a wider and more protracted protection from attack by fungi is given to plants treated with the new 1 , 2-dithiol-3-ones The new active substances also serve for the treatment of seeds without germination being adversely affected. For use in plant protection, the new active substances are worked up in the usual way with distributing and/or carrier substances and so used that the concentration of active substance li≤s between the limits of 0.01 and 2%. 1 , 2-dithiol-3-ones chlorinated in the 5-position such as 4,5-dichloro-1 , 2-dithiol-3-one (Deutsche Auslegeschrift DAS No. 1,102,174) and 4-aryl-5-chloro-l ,2-dithiol-3-ones (DAS No. 1,126,668) have already been described in the literature as pesticldal and fungicidal active substances. But these compounds are either inactive against phytopathogenic fungi and their spores or they are unsuitable as fungicides because of their phytotoxicity .

The following examples serve to illustrate the present invention. Parts and percentages are given by weight unless stated otherwise. The temperatures are given in degrees Centigrade .

Example 1 37.4 Parts of , 5-dichloro-l , 2-dithiol-3-one and 40 parts of benzene sulphinic acid sodium salt in 300 parts by volume of methanol are heated within 30 minutes to 60° while stirring.

Part of the product crystallises out during this time. To complete the reaction, the reaction mixture is left to stand for 2 hours at room temperature, after which 400 parts by volume of warm water (70°) are added. The reaction product is filtered off, washed with water and then dried. The yield of crude pro-duct is 56.8 parts = 97$ of the theoretical. After recrystalli-sation from ethanol, the 4-chloro-5-phenylsulphonyl-l , 2-dithiol-3-one obtained melts at 121°.

Example 2 A mixture of 9.3 parts of , -dichloro-l , 2-dithiol-3-one , 15 parts of 4-toluene sulphinic acid sodium salt and 50 parts by volume of water is brought within 2 hours from 50° to 95° while stirring. During the heating, the reaction product crystallises out. The reaction mixture is then filtered while still warm. The filter residue is washed with water and then dried. The yield of crude product is 14.1 parts = 2 of the theoretical. Recrystallised from ethanol, the 4-chloro-5-( 4 ' -tolylsulphonyl ) -1 , 2-dithiol-3-one obtained melts at 132°.

Example 3 28 Parts of 4 , 5-dichloro-l , 2-dithiol-3-one and 43 parts of β-naphthalene sulphinic acid sodium salt in 50 parts by volume of benzene and 100 parts of water are heated, while stirring, for 4 hours at 50 - 55° and then boiled for 3 hours. The reaction mixture is cooled to 0° and the precipitate formed is filtered off. The filter residue is washed with water and then dried.

Recrystallised from isopropanol, the 4-chloro-5- ( β-naphthylsulphonyl ) -1 ,2 -dithiol-3-one melts at 132°. Ί Example 4 4.65 Parts of 4 , 5-dichloro-l , 2-dithiol-3-one and 4 parts of β-phenylethane sulphinic acid sodium salt in 20 parts by volume of ethanol are boiled for 20 minutes while stirring. Water is then added to the reaction mixture and the reaction product which precipitates is filtered off. The filter residue is washed with water and then dried. The yield is 7.6 parts =95$ of the theoretical. The 4-chloro-5- ( β-phenylethyl sulphonyl ) -1 ,2 -dithiol-3-one melts at 137°.

Example 5 3 Parts of 4-(4 ' -tolyl) -5-chloro-l ,2-dithiol-3-one and 2.1 parts of crude thnqphene sulphinic acid sodium salt in 12 parts by volume of dimethyl sulphoxide are stirred at room temperature for 30 minutes and then 50 parts of ice water are added. The reaction product precipitates. To purify, it is boiled with 20 parts by volume of ethanol, whereupon it only partly dissolves, is again cooled and filtered. The yield of crude product is 3.3 parts = 76 of the theoretical. On recrystallisation from ben-zene/cyclohexane, the 4- ( 4 ' -tolyl) -5-[ thienyl-(2 ') -sulphonyl ] -l,2-dithiol-3-one melts at 132°.

Example 6 First, 4 parts of methane sulphinic acid sodium salt and then 5.8 parts of -4-phenyl-5-chloro-l , 2-dithiol-3-one are added to 30 parts of dimethyl formamide while stirring, the mixture being cooled with ice water. The reaction mixture is then stirred for 60 minutes at room temperatire whereupon 150 parts of ice w ter re dd d. Aft r h h ti crystallises out. After filtering off, it is washed with water and recrystallised from ethanol . Recrystallised from ethanol, the 4-phenyl-5-methylsulphonyl-l , 2-dithiol-3-one melts at 153°. The yield of crude substance is 4 parts = 58$ of the theoretical.

Example 7 7.0 Parts of 4, 5-dichloro-l ,2-dithiol-3-one and 10 parts of 4-acetamidobenzene sulphiric acid sodium salt are boiled for 45 minutes while stirring in 100 parts by volume of methanol.

The reaction mixture is then cooled and the precipitate formed is filtered off. The filter residue is washed, first with 50 parts by volume of hot methanol, then with 50 parts by volume of a mixture of methanol and water 1:1 and finally with water and dried. Recrystallised from ethylene glycol monomethyl ether (methyl cellosolve), the 4-chloro-5-( ' -acetamidophenylsulphonyl )-1 , 2-dithiol-3-one obtained melts at 234-236°. In order to saponify the acetamido group, 50 parts by volume of methyl cellosolve and 20 parts by volume of concentrated aqueous hydrobromic acid can be added to this substance. The mixture is kept for 2 1/2 hours at 70 - 75° while shaking now and then. A clear solution is obtained which is evaporated to dryness. Ice water is added to the residue and it is neutralised with a little sodium bicarbonate. The product which precipitates is filtered off under suction, washed several times with water and dried. The yield of crude product is 7.3 parts = 63% of the theoretical (calcu-lated on the 4 , 5-dichloro-l ,2-dithiol-3-one used). The 4-chloro-5-(4T-amino-phenylsulphonyl)-l,2-dithiol-3-one obtained in this way melts at 191 - 193° after recrystallisation from ethanol/ water .

On reacting a 4-chloro-, 4-alkyl- or 4-aryl-5-chloro-l , 2-dithiol-3-one with the salt of a correspondingly substituted sul- sulphonyl-1 , 2-dithiol-3-ones given in the following Table are produced . compound M.P. °C 4 -chloro-5-methylsulphonyl-1 , 2-dithiol-3-one 196 4 -chloro-5-ethylsulphonyl-l , 2-dithiol-3-one 122 4 -chloro-5-n-propyl sulphonyl-1 , 2-dithiol-3-one 77 4 -chloro-5-isopropyl sulphonyl-1 , 2-dithiol-3-one 126 4 -chloro-5-n-butylsulphonyl-1 ,2-dithiol-3-one 69 4 -chloro-5-chloromethyl sulphonyl-1 , 2-dithiol-3-one 136 4 -chloro-5-(2 ' -tolyl sulphonyl) -1 ,2-dithiol-3-one 107 4 -chloro-5- (2 ' , 5 ' -dimethylphenyl sulphonyl) -1 , 2-dithiol- 3-one 129 4 -chloro-5-(2 ' , 4 ' -dimethylphenylsulphonyl) -1 , 2-dithiol- 3-one 92 4 -chloro-5- ( 3 ' , 4 · -dimethylphenyl sul honyl) -1 , 2-dithiol- 3-one 147 4 -chloro-5- ( 2 ' , 4 ' ,6 ' -trimethylphenyl sulphonyl) -1 ,2-di- thiol-3-one 145 4 -chloro-5-( 4 ' -ethylphenyl sulphonyl) -1 , 2-dithiol-3-one 90 4 -chloro-5-(4 ' -isopropylphenyl sulphonyl) -1 ,2-dithiol-3- one 125 4 -chloro- - ( 4' -sec. -butylphenyl sulphonyl) -1 , 2-dithiol- 3-one 62 4 -chloro-5- ( 1 -chlorophenyl sulphonyl) -1 , 2-dithiol-3-one 192 4 -chloro-5- ( 2 ' , 5 ' -dichlorophenyl sulphonyl) -1 , 2-dithiol- 3-one 164 4 -chloro-5- (2 ' , 4 ' , 5 ' -trichlorophenylsulphonyl) -1 , 2-di- thiol-3-one 180 4 -chloro- - (2 ' , ' -dichloro- 1 -methyl-phenyl sulphonyl ) - 1 , 2-dithiol-3-one 182 4 -chloro-5- ( 31 -carboxyphenyl sulphonyl) -1 , 2-dithiol-3- one 255 4 -chloro-5- ( 4 ' -methox henylsulphonyl ) -1 , 2-dithiol-3-one 162 4 -chloro-5-benzyl sulphonyl-1 , 2-dithiol-3-one 139 4 -chloro-5-[ 5 ' ,6' ,7' ,8 ' -tetrahydronaphthyl- ( 2 ·) -sulphonyl ] -1 , 2-dithiol-3-one 148 4 -chloro- -[ hienyl-(2 ' ) -sulphonyl ] -1 , 2-dithiol-3-one 134 4 -phenyl-5-ethylsulphonyl-1 ,2-dithiol-3-one 113 4 -phenyl-5-phenyl sulphonyl-1 ,2-dithiol-3-one 117 4 -phenyl-5- ( ' -tolyl sulphonyl) -1 , 2-dithiol-3-one 133 4 -( ' -tolyl) - -methyl sulphonyl-1 ,2-dithiol-3-one 188 4 -(4 ' -tolyl) -5-phenyl sulphonyl-1 , 2-dithiol-3-one 141 Example 8 A mixture of 1.5 parts by volume of A0% aqueous peracetic acid and 15 parts by volume of glacial acetic acid are added dropwise within 1 hour to a solution of 1.18 parts of 4-chloro-5-(4'-chlorophenylthio)-l,2-dithiol-3-one in 80 parts by volume of glacial acetic acid, the addition being made while stirring at room temperature. The whole is then heated for 15 hours at 67 - 70°. The glacial acetic acid is then distilled off and the residue is recrystallised from ethylene glycol monomethyl ether. The melting point of the product obtained is 190° (indistinct). Chromatographic adsorption on silica gel in chloroform yields pure 4-chloro-5-( 4 ' -chlorophenyl sul honyl) -1 , 2-dithiol-3-one from it. The pure product melts at 192°.

Example 9 1300 Parts by volume of an about 40 solution of peracetic acid in acetic acid are added within 30 hours to a suspension of 638 parts of ( 4-chloro-l , 2-dithiol-3-one-5-yl ) -ethyl -sulphide in 2000 parts by volume of glacial acetic acid, the addition being made while stirring at a inner temperature of 30 - 35°. The whole is then stirred for a further 20 hours at room temperature and cooled afterwards at 10°. The crystalline reaction product is filtered off, washed several times with methanol and finally dried in the air. The yield is 550 parts = 75$ of the theoretical. The 4-chloro-5-ethylsulfonyl-l , 2-dithiol-3-one obtained in this way melts at 122°.

The following compounds may be obtained in the manner described in Examples 1 - 9: 4-chloro-5-(2 ' -chlorobenzyl sulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-( ' -chlorobenzyl sulphonyl ) -1 , 2-dithiol-3-one 4-chloro-5-( ' -bromobenzyl sulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-[naphth-(l ' ) -ylmethyl sulphonyl ] -1 ,2-dithiol-3-one 4-(4 ' -chlorophenyl) -5-methylsulphonyl-1 ,2-dithiol-3-one 4-(4 ' -tert . butylphenyl) -5-methyl sulphonyl-1 ,2-dithiol-3-one 4-chloro-5-carboxymethylsulphonyl-l ,2-dithiol-3-one 4-chloro-5-(methoxycarbonyl-methylsulphonyl) -1 ,2-dlthiol-3-one 4-chloro-5-(2 * -methoxy-ethyl sulphonyl) -1 ,2-dlthiol-3-one 4-chloro-5-(2 ' -acetamldo-ethylsulphonyl) -1 ,2-dithiol-3-one 4-chloro-5-(2 -diethylamino-ethylsulphonyl) -1 ,2-dithiol-3-one 4-chloro-5-(2» -p-tolyl-ethylsulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-(2 ' -p-chlorophenyl-ethylsulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-(2 ' -hydroxy-5 ' -nitrophenylsulphonyl) -1 ,2-dithiol-3- one 4-chloro-5- ( 2-cyanophenylsulphonyl) -1 ,2-dithiol-3-one 4-chloro-5-[ 2 ' -bromonaphthyl- (1 ' ) -sulphonyl ]-l ,2-dithiol-3-one 4-chloro-5-( 31 -methyl-4 ' -ethoxycarbonyl-phenylsulphonyl) -1 ,2- dithiol-3-one 4-chloro-5-(4 ' -n-nonyl henylsulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-(4 ' -phenoxyphenylsulphonyl) -1 ,2-dithiol-3-one 4-chloro- -biphenyl sulphonyl-1 , 2-dithiol-3-one 4-chloro-5- ( 41 -ethylthiophenylsulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-C4 ' -dimethylamino-phenylsulphonyl) -1 , 2-dithiol-3-one 4-chloro-5-n-hexylsulphonyl-l , 2-dithiol-3-one .

The activity of the new 5-sulphonyl-l ,2-dithiol-3-ones of general formula I against spores of phytopathogenic fungi was determined by germination test on the spores of the following types of fungi: Alternaria tenuis Botrytis cinerea Calsterosporium c.

Coniothyrium dipl.

Fusarium clumorum Mucor spec.

Penicillium spec.

Stemphylium cons. 1 ccm of a 1$, 0.1% and 0.01% acetone solution of the active substance is placed on 2 glass slides (26 x 76 mm), under the same conditions. The solvent is evaporated off and a uni- form coating of active substance is obtained on the glass slides The slides are inoculated with spores of the above fungi and then kept in dishes at room temperature in an atmosphere which is almost saturated with steam. The germinated spores are counted twice, first after 2 - 3 days and the second time after 4 - 6 days. The average is formed from the two values obtained. The results are summarised in the following Table. + means an at least 90% inhibition of germination effected by the residue of 1 ccm of a 1% solution of active substance , ++ means the same inhibition effected by the residue of 1 ccm of a 0.1$ solution of the active substance, +++ means the inhibition effected by the residue of lccm of a 0.01$ solution of active substance, - means no inhibition of germination with the concentrations used. compound . 4-chloro-5-methyl sulphonyl-1 , 2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5-ethyl sulphonyl-1 , 2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5-n-propylsulphonyl-l ,2-dithlol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5-isopropylsulphonyl-1 ,2 dlthlol-3-one + Alt tiiernraaensu+ + ++ ++ + ++ ++ ++ 4-chloro-5-phenyl sulphonyl-1 , 2- Bttiiorsyn cerea dlthlol-3-one ++ ++ ++ ++ ++ ++ ++ ++ Cltisaerosporum c. 4-chloro-5- ( 2 ' -tolylsulphonyl ) -1 ,2-dithiol-3-one +++ +++ +++ +++ +++ +++ +++ +++ Cthi dliinooyrump. 4-chloro-5- ( ' -tolyl sulphonyl) -1 ,2-dithiol-3-one ++ ++ ++ ++ + Flisuraumu cn.+ ++ ++ ++ 4-chloro-5-( 4 ' -sec . -butylphenyl-sulphonyl) -1 ,2-dithlol-3-one +++ + +++ +++ + +++ +++ +++ 4-chloro-5-(2 ' , 5 ' -dimethylphenyl- P Iliiinecu smpec. sulphonyl ) -1 , 2-dithlol-3-one ++ ++ ++ ++ ++ ++ ++ ++ Stlhiepyum cons. 4-chloro-5-(21 , ' -dimethyl-phenyl sulphonyl) -1 , 2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5-( ' -aminophenylsulphor yl) -1 , 2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5-benzylsulphonyl-1 ,2-dithiol-3-one +++ +++ +++ +++ +++ - +++ +++ 4-chloro-5- ( β-phenylethyl sulphonyl) -1 ,2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-chloro-5- ( β-naphthyl sulphonyl) -1 , 2-dithiol-3-one ++ ++ ++ ++ ++ + ++ + -phenyl-5-methyl sulphonyl-1 , 2-dithiol-3-one ++ ++ ++ ++ ++ ++ ++ ++ 4-phenyl-5-methyl sulphonyl-1 , 2-dithiol-3-one ++ ++ +++ +++ ++ ++ ++ +++ , 5-dichloro-1 , 2-dithiol-3-one DAS 1 102 174 The phytofungicidal activity was determined by comparative tests on beans.

Leaves of bean plants (Phaseolus vulgaris) in the twoleaf stage were sprayed with an aqueous suspension containing 0.1% of active substance.

The suspension was obtained from a 10$ wettable powder by dilution with water. After drying, the leaves were infested with a fresh suspension of spores of Uromyces appendiculatus , left for 1 day, in a moist room and then kept in a. greenhouse . The test was evaluated after 7 to 10 days, according to the following comparative scale: 0 no infestation 1-9 inhibition of infestation according to its extent inactive x leaves damaged (burned place or zone) xx up to 1/3 of the leaf surface damaged XXX more than 1/3 of the leaf surface damaged or leaf and plant respectively destroyed compound result 4 -chloro-5 -methyl sulphonyl-1 , 2-dithiol-3-one 0 4 -chloro-5 -ethylsulphonyl-1 , 2 -dithiol-3-one 1 4 -chloro-5 -n-butylsulphonyl-1 , 2-dithiol-3-one 2 4 -chloro-5 -chloromethyl sulphonyl-1 , 2-dithiol-3-one 0 4 -chloro-5 -phenylsulphonyl-1 , 2-dithiol-3-one 0 4 -chloro-5 -(21 , 4 ' -dimethyl henyl sulphonyl) -1 , 2-dithiol- 3-one 1 4 -chloro-5 -(2 ' -phenylethyl sulphonyl) -1 ,2-dithiol-3-one 1 4 -chloro-5 -thienylsulphonyl-1 , 2-dithiol-3-one 2 compound result 4-phenyl-5-(4 '-tolyl sulphonyl) -1 ,2 -dithiol-3-one 2 4-( 4 ' -tolyl) -5-methylsulphonyl—1 ,2-dlthlol-3-one 2 4,5-dichloro-l,2-dithiol-3-one (DAS 1.102.174) 10 4-phenyl-5-chloro-l,2-dithiol-3-one (DAS 1.126.668) XX 4-(4'-tolyl)-5-chloro-l,2-dithiol-3-one (DAS 1.126.668) XXX In addition, the new 5-sulphonyl-l ,2-dithiol-3-ones of the general formula I have properties which, apart from plant protection, also made them valuable for the combatting of microorganisms which injure and destroy organic materials and objects for use and for the protection of such materials against the attack of said microorganisms. By such microorganisms are meant fungi and bacteria which attack, in particular, keratinic, cellulose-containing synthetic materials (wood, fabrics, leather etc.) and coating materials. The materials given above and objects made therefrom are given a good and protracted protection by impregnating them with solutions or dispersions of active substance having a content of active substance of at least 1 g/litre. For this purpose, the active substances can also be applied in combination with other substances suitable for the protection of the materials.

The action on bacteria was ascertained by means of the following bacteriostatic test on the following strains of bacteria: staphylococcus aureus SG 511, Escherichia coli NCTC 8196, Bacillus pumilus.

"The Agar incorporation test" according to Leonard and Blackford was used as test method. Nutrient agar plates containing 100, 30, 10 and 3 ppm of active substance (ppm means parts of active substance per 10 parts of diluent) are inoculated with solutions of the above strains and incubated 2 x 24 hours at 37° . The marginal concentrations inhibiting the growth of individual strains are given in the followin Table: The fungistatic activity of 5-sulphonyl-l , 2-dithiol-3-ones of the general formula I, prepared according to the inven-tion, was determined by means of the following test: 3 Parts of active substance were dissolved in 5 parts of a mixture (1:1) of dimethyl formamide and ethylene glycol mono-methyl ether. 87 Parts of a commercial dispersion colour based on polyvinyl acetate-ethyl acrylate copolymer were stirred in, 5 parts of water were added and the whole was stirred until homogeneity is attained. Two other solutions were prepared in exactly the same way except that one contained 1 part of active ingredient and 89 parts of the commercial dispersion colour and the other contained 0.3 parts of active ingredient and 89.7 parts of dispersion colour. In this way, three ready-for use paints were obtained which contained 3, 1 and 0.3% by weight of active ingredient respectively. laying them on filter paper, e.g. Whatman 3 MM and by exposing the papers so prepared, first for 3 days at 20°C and then for 8 days at 65°C and 80 - 90% relative humidity.

Circular samples of 2 cm diameter were cut from these filter papers and laid in Petri dishes (painted side upwards) on 3 cm of Sabouraud-Maltose agar inoculated with spores of Peni- cillium cyclopium and then stored for 7 days at 28°C. The following Table shows the concentrations of active substance with which no mould was formed either on the upper or lower surface of the papers.

The bactericidal and fungicidal action of the 5- sulphonyl- 1 , 2-dithiol-3-ones obtained according to the invention were tested by dissolving 25 g of the active substance to be tested in 1 litre of ethylene glycol monomethyl ether. Strips of cotton fabric which had been washed at the boil (about 85 g/sq. m.) are tent of 40$ by weight, so that the concentration of active substance on the fabric is 1% by weight. The strips of fabric are dried for 5 minutes in a stream of steam after which they are washed twice for 15 minutes each time with a soap solution (5 g soap/litre ' of water) at 40°C, then rinsed twice for 3 minutes each time with cold water and dried. The following tests were then made with the strips of fabric so treated: a) Inhibition test Circular samples of 2 cm diameter of said fabric were placed in Petri dishes on agar culture medium which had been inoculated in the usual way with A) Staphylococcus aureaus SG 511 B) Escherichia coli NCTC 8196 C) Aspergillus niger ATCC D) Candida albicans The dishes containing agar A), B) and D)'were stored for 24 hours at 37° and C) for 3 days at 28°. The effectiveness of the active substances was determined by counting the number of germs and colonies growth either on or under the samples. b) Maceration test Circular samples of 4 cm diameter of the fabric treated as described above were subjected to maceration in compost consistin of 50$ cow dung, 30$ compost and 20% sand (all % by weight).

The earth had 30% relative humidity and is kept at 28°C. After 10 days, the samples were disinterred, cleaned and conditioned at 24°C and 65% relative humidity. The tensile strength after the maceration was compared with that of the fabric after the treatment above described which had been determined before the maceration and expressed in percentages of the initial tensile c) Mildew spot test Circular samples of 8 cm diameter of the fabric treated as described above were placed on sterile Worth agar plates prepared according to Difco Manual, 9th Edition p. 244 by spreading 15 ml of Worth agar in Petri dishes of 10 cm diameter and leaving them to solidify.- The samples were placed on the agar which was then inoculated with a spore suspension containing spores of the fungi Chaetomium globosum, Aspergillus niger and Trichoderma viride.

The Petri dishes were stored for 5 days at 28°C and then the growth of mould was determined.

Results ; a) Inhibition test In the following table the abbreviations signify: + = growth of bacteria and fungi on and under the fabric sample - = no growth A = Staphylococcus aureus SG 511 B = Escherichia coli NCTC 8196 C - Aspergillus niger ATCC D = Candida albicans compound A B C D 4-chloro-5-methyl sulphonyl-1 , 2-dithiol-3-one _ _ _ 4-chloro-5-n-butylsulphonyl-l , 2-dithiol-3-one - - - - 4-chloro-5- (2 ' -tolyl sulphonyl) -1 ,2-dithiol-3one - - - - 4-chloro-5- ( ' -aminophenyl sulphonyl) -1 , 2-dithiol- 3-one _ _ — _ 4-chloro-5-( 3 ' -carboxyphenylsulphonyl) -1 ,2-dithiol- 3-one _ _ 4-chloro-5-( 2 ' , ' -dichlorophenyl sulphonyl) -1 , 2-di- thiol-3-one - - - - compound A B C D 4-chloro-5- (β-phenylethyl sulphonyl) -1 ,2-dithiol-3- one 4-chloro-5-[ thienyl-(2 ' ) -sulphonyl ]-l , 2 -dithiol-3- one — _ — — 4-phenyl-5-methyl sulphonyl-1 , 2-dithiol-3-one - - - - 4,5-dichloro—1 , 2-dithiol-3-one (DAS 1.102.174) - - + + 4-phenyl-5-chloro-l,2-dithiol-3-one (DAS 1.126.668) + + + + b) Maceration test compound Residual tensile stiength in % 4 -chloro-5-methylsulphonyl-1 ,2-dithiol-3-one 100 4 -chloro-5-ethyl sulphonyl-1 ,2-dithiol-3-one 97 4 -chloro-5- ( 41 -sec . -butylphenylsulphonyl) -1 ,2-di- thiol-3-one 100 4 -chloro-5-(2 ' , 4 ' -dimethylphenylsulphonyl ) -1 ,2-di- thiol-3-one 100 4 -chloro-5- (2 ' , 4 ' , 6 ' -trimethylphenyl sulphonyl) -1,2- dithiol-3-one 100 4 -chloro-5-(2 ' ,5' -dichlorophenyl sulphonyl) -1 , 2-dithio 3-one 100 4 -chloro-5-benzyl sulphonyl-1 ,2 -dithiol-3-one 100 4 -chloro-5-( β-phenyl-ethylsulphonyl)-l , 2-dithiol - 3-one 100 4 -chloro-5-( β-naphthylsulphonyl) -1 , 2-dithiol-3-one 100 4 ,5-dichloro-l,2-dithiol-3-one (DAS 1.102.174) 29 4 -phenyl-5-chloro-l,2-dithiol-3-one (DAS 1.126.668) 0 c) Mildew spots test no growth of mildew spots and mould few mildew spots and little mould growth medium degree of mildew spots and mould growth many mildew spots and strong mould growth compound results 4 -chloro-5-methyl sulphonyl-1 , 2-dlthiol-3-one 0 4 -chloro-5-ethylsulphonyl-1 , 2 -dithiol-3-one 0 4 -chloro-5-(2 ' -tolylsulphony]-l ,2-dithiol-3-one 0 4 -chloro-5-(4 ' -tolyl sulphonyl) -1 , 2-dithiol-3-one 0 4 -chloro-5-(2 ' , 41 -dimethylsulphonyl )-l , 2-dithiol-3-one 0 4 -chloro-5-( 4 ' -ethylphenyl sulphonyl) -1 , 2-dithiol-3-one o · 4 -chloro-5- ( 4 ' -sec . -butyl henyl sulphonyl ) -1 , 2-di- thiol-3-one 0 4 -chloro-5-(2 ' , 5 ' -dichlorophenylsulphonyl) -1 , 2-dithiol- 3-one 0 4 -chloro-5-(3 ' -carboxyphenylsulphonyl) -1 , 2-dithiol-3- one 0 4 -chloro-5- (β-phenylethyl sulphonyl) -1 , 2-dithiol-3-one 0 4 -chloro-5-benzylsulphonyl-1, 2-dithiol-3-one 0 4 -phenyl-5-methyl sulphonyl-1 ,2-dithiol-3-one 0 4 ,5-dichloro-l ,2-dithiol-3-one (DAS 1.102.174) +++ 4 -phenyl-5-chloro-l,2-dithiol-3-one (DAS 1.126.668) +++ The fungicidal and bactericidal agents according to the invention are produced in the known way by intimately mixing and milling active ingredients of general formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. These agents can be made up into and used in the following forms: Solid forms: dusts, sprinkling agents, granulates such as coated granules, impregnated granules, homogeneous granules; Water dispersible concentrates of active substances: wettable powders, pastes, emulsions; Liquid forms: solutions and aerosols.

To produce the solid forms for use (dusts, sprinkling carriers. Examples of carriers are kaolin, talcum, bole, loess, chalk, limestone, ground limestone, ataclay, dolomite, distoma-ceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica) , calcium and magnesium sulphates, magnesium oxide, milled synthetic plastics, fertilisers such as ammonium sulphate, ammonium phosphates, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal etc.

These carriers can be used alone or admixed with each other.

The particle size of the carriers is, for dusts up to about 100 i , for sprinkling agents from about 75 p - 0.2 mm and for granulates from 0.2 mm - 1 mm or coarser.

As a rule, the concentrations of active substances in the solid preparations is from Ό.5 - 80$.

To these mixtures can also be added additives which stabilise the active substance and/or non-ionogenic , anionically and cationically active substances which, for 'example, improve the adhesion of the active substances on plants and parts of plants (glues and adhesives) and/or attain better wettability (wetting agents) and dispersibility (dispersing agents) of the active substances. Examples of adhesives' are as follows: olein/ chalk mixture, cellulose derivatives (methyl celluloses, carboxy-methyl celluloses) , hydroxyethyl glycol ethers of mono- and di-alkyl phenols having 5 - 15 ethylene oxide radicals per molecule and 8 - 9 carbon atoms in the alkyl radical, lignin sul-phonic acids, alkaline and alkaline earth salts thereof, polyethylene glycol ethers (Carbowaxes) , fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per mole-cule and 8 - 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl formaldehyde as well as Latex products.

The concentrates of active substance which can be dispersed in water (wettable powders), pastes and emulsion concentrates, are agents which can be diluted with water to any concentration de-sired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface active substances, and anti-foam agents and, optionally, solvents. The concentration of active substance in these agents is 5 - 80%.

Wettable powders and pastes are obtained by mixing and milling the active substances with dispersing agents and pulverulent carriers in suitable mixers and milling machines until homogeneity is attained. Carriers are, for example, those mentioned in the paragraph dealing with solid forms for application. In some cases it is advantageous to use mixtures of different car-riers. Examples of dispersing agents which can be used are: condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives and formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde as well as alkali, ammonium and alkaline earth salts of lignin sulphonic acid, further, alkylaryl sulphonates, alkali and alkaline earth salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols , heptadecanols, octadecanols , octacteenols and salts of sulphated fatty alcohol polyglycol ethers, the sodium salt of oleoyl ethion-ate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth salts.

Silicones, "Antifoam A" etc. are examples of antifoaming agents.

The active substances are so mixed, milled, sieved and strained with the additives mentioned above that, in wettable 3 fx, is not exceeded. To' produce emulsion concentrates and pastes, dispersing agents such as those given in the previous paragraphs, organic solvents and water are used. Examples of solvents are as follows: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide and mineral oil fractions bQiling between 120 and 350°. The solvents must be almost without smell, not phytotoxic, inert to the active substances, and not easily inflammable.

In addition, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of general formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes alone or mixed with each other can be used as organic solvents.. The solutions contain tte active substances in a concentration from 1 to 20% .

The agents according to the invention described can be mixed with other biocidally active compounds or agents. Thus, to broaden the range of action, the new agents can contain, e.g. insecticides, other fungicides, bactericides, fungistatics, bacteriostatics or nematicides in addition to the compounds mentioned of general formula I. The agents according to the invention can also contain fertilisers, trace elements etc.

The following forms for application of the agents accord-ing to the invention serve to illustrate the applicative aspect of the present invention; where: not otherwise expressly stated, parts are given as parts by weight.

Dust s To produce a) a 10?? and b) a 2% dust, the following components are used: a) 10 parts of -chloro-5-phenylsulphonyl-1 , 2-dithiol-3-one parts of highly dispersed silicic acid 85 parts of talcum b) 2 parts of 4-chloro-5-(2 ' , 51 -dimethylphenylsulphonyl) - l,2-dithiol-3-one 1 part of highly dispersed silicic acid 97 parts of talcum.

The above active substances are intimately mixed and milled with the carriers. The fungicidal dusts so obtained serve for the treatment of seed beds or for the dusting of plants.

Seed dressings To produce a) a 10$ and b) a 60$ seed dresssing, the following components are used: a) 10 parts of 4-chloro-5-methylsulphonyl-l ,2-dithiol-3-one parts of kieselguhr 1 part of liquid paraffin 84 parts of talcum b) 60 parts of 4-phenyl-5-methylsul honyl-1 , 2-dithiol-3-one parts of kieselguhr 1 part of paraffin (liquid) 24 parts of talcum.

The active substances mentioned are intimately mixed in a mixer with the carriers given and the paraffin as distributing agent and then milled. The pulverulent seed dressings obtained serve for the treatment of seeds of all types.

Granulates To produce a) a 2.5% and b) a 5% granulate, the following components are used: a) 2.5 parts of -phenyl-5-methyl sulphonyl-1 , 2-dithiol-3-one 2.5 parts of kieselguhr parts of polyethylene glycol 89.3 parts of ground limestone (0.4 - 0.8 mm diameter) 0.7 parts of silicic acid b) 5 parts of 4-chloro-5.-n-butylsulphonyl-l , 2-dithiol-3-one 1.5 parts of kieselguhr 0.5 parts of cetyl polyglycol ether 87 parts of ground limestone parts of polyethylene glycol 1 part of silicic acid.

The ground limestone in each formulation is impregnated with the polyethylene glycol or with the cetyl polyglycol ether and then mixed with a mixture consisting of the active substance given, the silicic acid and the kieselguhr. These granulates are particularly suitable for the disinfection of seed beds.

Wettable powders To produce a 10% wettable powder, the following components are used: parts of 4-chloro-5-chloromethylsulphonyl-l , 2-dithiol- 3-one parts of sodium lignin sulphonate 2 parts of a finely milled mixture of kaolin and polyvinyl alcohol (1:1) parts of kieselguhr 38 parts of kaolin The active substance mentioned is mixed and finely milled with the carriers and distributing agents. A wettable powder having excellent wettability and suspendibility is obtained.

Suspensions of any concentration of active substance desired can be obtained from such wettable powders by dilution with water. Such suspensions serve for the treatment of cultivated plants and of materials and objects which are subject to attack by fungi and bacteria.

Emulsion concentrates To produces a) a 5 , b) a 10% and c) a 15% emulsion concentrate, the following components are used: a) 5 parts of 4-chloro-5-phenylsulphonyl-l , 2-dithiol-3-one 40 parts of dimethyl formamide 50 parts of petroleum (boiling range 230 - 270°) parts of a composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensation product of ethylene oxide and ricinus oil (e.g.

"Emullat WK", Union Chimique Beige, S.A., Brussels) b) 10 parts of 4- ( 4 ' -tolyl ) -5-methylsul honyl-l , 2-dithiol- 3-one parts of dimethyl formamide 50 parts of petroleum (boiling range 230 - 270°) parts of a composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensa- tion product of ethylene oxide and ricinus oil (e.g.

"Emullat WK" , Union Chimique, S.A., Brussels) c) 15 parts of 4-chloro-5- (β-naphthyl sulphonyl ) -1 , 2-dithiol- 3-one 27 parts of dimethyl formamide parts of a composite emulsifyer consisting of the Ca salt of dodecylbenzene sulphonic acid and a condensation product of ethylene oxide and ricinus oil (e.g.

"Emullat WK", Union Chimique, S.A., Brussels).

The active substance concerned is dissolved in petroleum or dimethyl formamide and then the composite emulsifyer is added to this solution. Emulsion concentrates are obtained which can be diluted with water to any concentration desired. Such emulsions are suitable for the treatment of cultivated plants. - 29 - 25982/2

Claims (15)

1. New 5-sulphonyl-l, 2-dithiol-3-ones of the general formula I: wherein R-^ represents halogen, phenyl or lower alk l-substituted phenyl, and represents a straight or branched alkyl radical, optionally mono- or poly-substitutcd by halogen, hydroxyl, carboxyl, alkoxy-carbonyl, phenyl, alkoxy, acylamino, alkylamino, dialkylamino, alkylphenyl or halogenphenyl; an aromatic radical optionally mono- or poly-substituted by hydroxyl, amino, nitro, cyano, carboxyl, carbamoyl, halogen, alkyl (straight or branched chain) having 1 to 9 carbon atoms, phenyl, phenoxy, alkoxy, alkylamino, dialkylamino or alkanoylamino; or the thienyl radical.

2. The compound 4-chloro-5-methylsulphonyl-l, 2-dithiol- 3-one.

3. •3. The compound 4-chloro-5-ethylsulphonyl-l, 2-dithiol-3- one. · ,

4. The compound 4-chloro-5- ( ' - tolylsulphonyl)-l, 2-dithiol- 3-one.

5. The compound 4-chloro-5- (2 ' , 4 ' -dimethylphenylsulphonyl '' ' l,2-dithiol-3-one.

6. . The compound 4- chIoro-.5-benz ls l h h - - - 30 25982/2

7. The compound 4-phenyl-5-methylsulphonyl-1 , 2-dithiol-3-one ,

8. 3. .Process for the production of new 5-sulphonyl-l , 2-di- thiol-3-ones of general formula I wherein 2^ represents halogen, phenyl or lousr alkyl-subst tu ed phenyl, aiad represents a straight or branched alkyl radical, optionally mono- or poly-substituted by halogen, hydrosyl, carboxyl, alkoxy-carbonyl, phenyl, alkoxy, acylamino, alkylamino, dialkylamino, alkylphenyl or halogenphenyl; an aromatic radical optionally mono- or poly-substituted by hydroxyl, amino, nitro, cyano, carboxyl, carbamoyl, halogen, alkyl (straight or branched chain) having 1 to 9 carbon efcoms, phenyl, phenoxy, alkoxy, alkylamino, dialkylamino or alkanoylamino; or thienyl radical which comprises reacting a 1, 2-dithiol-3-one of general formula II wherein ^ has the meanings given above and X represents -a halogen atom, with a sulphinic acid salt of general formula III R2 - S02 - Q i wherein Rg has the meanings given above and Q represents the equivalent of a metal atom cation or the ammonium ion optionally in the presence of a solvent or diluent.

9. Process for the production of new 5-sulphonyl-1, 2-dithiol- 3-ones of the general formula I given in claim 1, characterised by oxidising a sulphide of 1, 2-dithiol- 3-one of the general formula IV wherein R-^ and have the meanings given in formula I in claim 1, by means of an oxidising agent, to form a sulphonyl compound of the general formula I defined in claim 1.

10. Fungicidal composition comprising as active substance, a 5-sulphonyl-l, 2-dithiol- 3-one of the general formula I defined in claim 1, in admixture with acceptable carriers therefor .

11. = Fungicidal and bactericidal composition comprising, as active substance, a 5-sulphonyl-l, 2-dithiol- 3-one of the general formula I defined in claim 1, in admixture with acceptable carriers therefor.

12. Process for the production of fungicidal compositions according to claim 10, which comprises mixing a 5-sulphonyl- 1 , 2-dithiol- 3-one of the general formula I defined in claim 1 with an acceptable carrier therefor.

13. Process for the production of fungicidal and bactericidal compositions according to claim 11, which comprises mixing a 5- sulphony1-1 j 2-dithiol- 3- one of the general formula I defined in claim 1 with an acce table carrier therefor.

14. Process for combatting phytopathogenic fungi which comprises contacting plants or parts thereof with a 5-sulphonyl-1, 2-dithiol- 3-one of general formula I defined in claim 1 or with compositions according to claim 10.

15. Process for combatting fungi and bacteria which injure and destroy organic materials and objects and for the protection of these materials and objects from attack by such microorganisms which comprises contacting plants, parts thereof or organic materials and objects with a 5-sulphonyl-l, 2-dithiol-3-one of general formula I defined in claim 1 or with compositions according to claim 11. 0ΑΤ» TMit 16TM OAT OF JUHE 966. on. fteitwo ». W